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Hong Wang1, Yingxu Wei2, Cecil ODell1, Zhongmin Liu2 and James P. Lewis1 1Department of Physics, West Virginia University, Morgantown, WV 2Dalian Institute of Chemical Physics, Dalian, P. R. China
Introduction
Zeolite is a broad term used to describe a family of microporous aluminosilicate minerals. Contain small pores and large surface area Constructed of AlO4-5 and SiO4-4 groups bound by oxygen Zeolites are synthesized by manipulating:
Structure Silica-Aluminum Ratio Pore Size Density
"Green Chemistry with Zeolite Catalysts." Chemical Engineering, The Chemical Engineers'Resource Page, Distillation, Heat Transer, Design, Spreadsheet Solutions, Departments, Chemistry. Web. 22 Apr. 2010. <http://www.cheresources.com/zeolitezz.shtml>.
http://s3.amazonaws.com/memebox/uploads/3562/kanatzidis-gasNorthwester.jpg
Coal
Natural Gas
Synthesis Gas
Methanol
MTO
Z-H +n(CH3OH)
Olefins
Z-H: ZSM-5 catalytic zeolite 1977, Chang, Lang and Silvestri, US patent 4062905
https://mailhost-2.tamu.edu/service/home/~/Zeolite_seminar.pdf?auth=co&loc=en_US&id=46940&part=5
Pore size around Strong acid sites Low selectivity in light olefins High selectivity
Al Al Si Al
P Al P
Al P Al Al (Al-O)3-Si
H O
Al-(O-P)3
0.43n m
Small size pores Suitable acid sites Strong stability High selectivity
Al Al Si Al
P Al P
Al P Al Al (Al-O)3-Si
H O
Al-(O-P)3
SM1: Al Si (not yield) SM2: P Si, H SM3: Al,P Si,Si Acidity: Si(4Al)<Si(3Al)<Si(2Al)<Si(1Al) Nonuniformed Silicon Incorporation
J. Tan, Z. M. Liu, X. H. Bao, X. C. Liu, X.W. Han, C. Q. He, R. Z. Zhai, Microporous and Mesoporous Mateirals 53 (2002), 97 (108)
Substantial computational time involved Extensive possibilities of silicon incorporation into a larger framework Identify optimal acid sites with a variety of silicon-incorporating environments Unravel the puzzle of silicon incorporation trends during the SAPO-34 crystallization process and accompany the experimental design with a full-knowledge framework.
Rhombohedral unit cell 12 tetrahedral (T) sites- 6 Al & 6 P Space Group: R3 [AlPO4]+(n+m)Si4++(m-n)H+
2x2x2 supercell (288 atoms total) 96 tetrahedral (T) sites- 48 Al & 48 P Space Group: P1 (after silicon substitution) [(n+m)Si,(m-n)H]nAl,mP+mP5++nAl3+
Fast Computational Approach to Evaluation of Material Properties and Chemical Reactivity: Ab initio DFT (FIREBALL)
Pseudopotentials, density-functional theory multi-center approximations Local excited" orbitals (fireball or Sankey-Niklewski orbitals) Atom in the box Fermi compression finite wavefunction Linear-scaling, massively-parallel molecular-dynamics capabilities simulate 1000s of atoms
J.P. Lewis et al., Phys. Rev. B. 64, 195103 (2001) S.D. Shellman et al., J. Comp. Phys. 188, 1-15 (2003) P. Jelinek et al., Phys. Rev. B. 64, 235101 (2005) J.P. Lewis et al., Phys. Stat. Sol. B. 248, 1989-2007 (2011)
108 167
49
213
361 364
Al,5P
Clustering/Energy Correlation
108 167
49
213
361 364
(2Al, P)
Si
Si Si triplet
Clustering/Energy Correlation
108 167
49
213
361 364
(2Al, P)
Si
Si Si triplet
4 (P
Si)
Si(4Al)
What we see ..
Higher clustering factors mean that the silicon incorporation in the framework is spread throughout the entire supercell. Silicon substitution of Al, P pair is a common trend for our random silicon incorporation calculations and these pairs lower the binding energy. In our low concentration incorporation (6 out of 96 possible sites), silicon prefers to form short range clusters.
structure No. 364
Acknowledgements
WVU HPC Supercomputering Facility Prof. Zhongmin Liu Dr. Yingxu Wei Dalian Institute of Chemical Physics, P.R.C
Thank you!